Europäisches Patentamt

(19) European Patent Office *EP000757704B1*

Office européen des brevets (11) EP 0 757 704 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.7: C08L 33/12, C08K 3/22
of the grant of the patent:
02.05.2001 Bulletin 2001/18 (86) International application number:
PCT/US96/01588
(21) Application number: 96906307.2
(87) International publication number:
(22) Date of filing: 05.02.1996 WO 96/26238 (29.08.1996 Gazette 1996/39)

(54) ACRYLIC SHEET HAVING UNIFORM DISTRIBUTION OF COLORING AND MINERAL FILLER
BEFORE AND AFTER THERMOFORMING
ACRYLPLATTE MIT GLEICHMÄSSIGER FARBSTOFF- UND MINERALFÜLLSTOFFVERTEILUNG
VOR UND NACH DER WÄRMEFORMUNG
FEUILLE ACRYLIQUE PRESENTANT UNE DISTRIBUTION UNIFORME DE LA COLORATION ET
DES CHARGES MINERALES AVANT ET APRES THERMOFORMAGE.

(84) Designated Contracting States: • WETTER, Carol, A.

AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL Richwood, KY 41094 (US)
PT SE
(74) Representative: Grünecker, Kinkeldey,
(30) Priority: 23.02.1995 US 392650 Stockmair & Schwanhäusser Anwaltssozietät
Maximilianstrasse 58
(43) Date of publication of application: 80538 München (DE)
12.02.1997 Bulletin 1997/07
(56) References cited:
(73) Proprietor: Aristech Acrylics LLC EP-A- 0 639 539 US-A- 3 847 865
Florence, Kentucky 41042 (US) US-A- 4 107 135 US-A- 4 145 477
US-A- 4 183 991 US-A- 4 413 089
(72) Inventors: US-A- 4 948 546 US-A- 5 242 968
• MINGHETTI, Ettore
Florence, KY 41042 (US) • DATABASE WPI Week 8923 Derwent
• EITEL, John, E. Publications Ltd., London, GB; AN 89-169865
Florence, KY 41042 (US) XP002041003 & JP 01 111 756 A (ASAHI CHEM
IND CO LTD) , 28 April 1989
EP 0 757 704 B1

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 0 757 704 B1

Description

[0001] This invention relates to the manufacture of acrylic sheet or slabs, that is sheets or slabs of polymethylmeth-
acrylate ("PMMA"), of the type usable in or designed for architectural uses such as kitchen countertops and more
5 complex shapes. The sheets or slabs contain significant amounts of flame retardant minerals, typically alumina trihy-
drate, and almost always have colorants in them, frequently in imitation of natural minerals such as onyx, marble or
similar synthetic appearing solid color or patterned types having no visibly distinguishable particles. This invention
describes a sheet that can be heated and bent at a sharp 90° angle and/or that can be heated and vacuum formed
into shapes like sinks and bowls without a significant esthetic sacrifice. In addition, the sheets or slabs of this invention
10 display specific physical and other properties, like low flammability and minimal color changes after thermoforming;
the uniform distribution of flame retardant significantly improves the consistency of impact resistance.
[0002] Sheets and slabs of synthetic mineral appearing material are now commonly used as kitchen countertops
and interior and exterior decorative coverings of all kinds for buildings such as banks, air terminals and stores. Such
applications frequently require that the material be fabricated to fit custom designed areas, requiring in turn that the
15 slabs or sheets be butted together or otherwise joined in ways that juxtapose a cross section with a normal surface at
90°.
[0003] The fabrication process requires extensive time and specially trained craftsmen to be completed successfully,
since special tools and procedures are necessary. If a shaped, one piece part of continuous or monolithic material is
desired, such a part can only be produced by casting it in a mold cavity under special conditions. In addition to the
20 high costs of such a process and for the installation of the parts (fitting, gluing it in place to a flat sheet, and/or finishing,
for example,) there are often color differences between the cast bowl, for example, and the flat slab of the same material.
[0004] The sheet (the terms "sheet" and "slab" will be used interchangeably herein) of our invention can provide a
relatively complex finished part by a simple thermoforming operation -- that is, the sheet is heated and then pulled by
vacuum into a concave cavity (or convex) mold, where it is allowed to cool, to retain its new shape. Such a mold can
25 be shaped as a vanity top, with one 90° back splash wall, with a front end bull nose of 2.54 cm (1.0 inch) radius and
a vanity type bowl. After forming, cooling and trimming, the part can be installed directly in place, without additional
fabrication required.
[0005] Only one contemporary commercial product ("Corian" by DuPont) is said to be capable of being heat bent.
However, its performance is not suitable, for example, to make 90° angle back splash wall, since the minimum radius
30 of curvature specified by the "Corian" literature of which we are aware is (3.0 inches) 7.62 cm.
[0006] So far as we are aware, the use of alumina trihydrate in polymethylmethacrylate ("PMMA") articles was first
proposed by Stevens et al in U.S. Patent 3,563,939 (col. 4, lines 28-29) and Duggins in Canadian Patent 916,337. Its
flame retardant properties are now well known and accepted, and alumina trihydrate ("ATH") is now widely used as a
filler in various resinous products. Somewhat more detail for the construction of synthetic mineral products is provided
35 by Duggins in U.S. Patent 3,847,865; crosslinking agents are mentioned, for example. US-A-4, 107, 135 does not
disclose the amount of crosslinking agent in general terms. However, in Examples 1 to 5,1% of crosslinking agent,
based on the MMA syrup, is contained in the composition. Also proposed are mold release agents, and viscosity
reducers such as aliphatic acids.
[0007] Buser et al, in U.S. Patents 4,085,246 and 4,159,301 address the problem of the settling rates of various
40 particles used in making a simulated granite having a matrix of polymerizable methyl methacrylate ("MMA") having
PMMA dissolved in it. See column 7, lines 42-62 of US-A-4, 159, 301. They use the PMMA to adjust viscosity, which
in turn controls the settling rates of the larger particles -- see the Examples, particularly Example 5 of U.S. Patent
4,159,301, lines 31-34. They also use chain-transfer agents as accelerators for the polymerization -- col. 8, lines 58-68
of the same patent.
45 [0008] Uniformity of color is mentioned as a goal in Gavin et al U.S. Patent 4,413,089, wherein iron oxide pigment
of 10 microns or less is uniformly distributed in a syrup of MMA/PMMA which is then cured; prolonged storage of the
syrup is not recommended (col. 2, lines 50-64).
[0009] In addition to meeting the above-described challenges, a material destined for use as a kitchen countertop,
for example, should have a surface which is easily repairable and restored to its original appearance, such as by
50 sanding and polishing, be protected against flammability, and have good temperature resistance in spite of being
thermoformable.
[0010] The prior art has more or less neglected the goal of thermoformability or thermobending of solid surface
sheets, since the prior art products were generally designed for reproducing the look of flat, natural, mineral based
sheets.
55 [0011] It is the object of the present invention to make mineral filled PMMA sheets that:

-- can be heat bent at relatively sharp angles,

-- can be thermoformed into shaped articles without losing the uniform appearance and properties of the top surface,

2
 EP 0 757 704 B1

-- can be thermoformed by vacuum into a single-profile mold, concave or convex, and do not require two matching
molds,
-- have only minor and tolerable color changes across the whole finished part, either less than Delta E - 2.0 by Cielab
or not easily discernible by the human eye,
5 -- have a thermoforming temperature low enough to avoid any significant loss of water from ATH filler during ther-
moforming, as is often the case for other thermoplastic materials,
-- have a Flame Spread Index, by the ASTM E-84 Tunnel Test, lower than 75 and a Smoke Index of 350 or less,
-- have the same impact resistance, by a falling weight method, measured from both the top side and the bottom side.

10 [0012] According the the present invention, the object is attained by a composition for making a thermoformable
sheet or slab comprising

(a) a syrup comprising at least 60% of methyl methacrylate having dissolved within it 10% to 25% uncrosslinked
polymethylmethacrylate having a weight average molecular weight in the range of 30,000 to 600,000, said syrup
15 having dispersed within it y parts by weight of chain terminator per 100 parts by weight of methylmethacrylate and
x parts by weight of crosslinking agent per 100 parts by weight of the monomers in the dispersion
wherein

x is 0.01 to less than 0.5 and

20 y is no greater than x + 0.2 and no less than 0.01; and

b) solid particulates which will pass through a sieve having openings of 90 µm (microns), said solid particulates
comprising 20% to 60%, based on the weight of the final composition, alumina trihydrate.

25 [0013] The present invention further provides a method of making a thermoformable synthetic mineral sheet or slab
comprising

(1) preparing a syrup of uncrosslinked polymethylmethacrylate having a weight average molecular weight in the
range of 30,000 to 600,000 dissolved in ethylenically unsaturated monomers of which at least 60% by weight are
30 methyl methacrylate,
(2) adding to and dispersing within said syrup

(a) y parts by weight of chain terminator per 100 parts by weight of methylmethacrylate and x parts by weight
of crosslinking agent per 100 parts by weight of the monomers in the dispersion
35 wherein

x is 0.01 to less than 0.5 and

y is no greater than x + 0.2 and no less than 0.01; and

40 (b) solid particulates which will pass through a sieve having openings of 90 µm (microns), said solid particulates
comprising 20% to 60%, based on the weight of the final composition, alumina trihydrate,

(3) confining said syrup in a sheet forming mold, and

(4) polymerizing said ethylenically unsaturated monomers in said syrup in the presence of said crosslinking agent
45 and said chain terminator to form a solid sheet having a substantially fine-grained appearance.

[0014] The present invention provides for the stability of the suspension of alumina trihydrate (ATH) in a syrup of
methyl methacrylate having polymethylmethacrylate dissolved in it by maintaining the following ingredients within the
indicated ranges (by weight):
50
-- Content of PMMA dissolved in MMA/other monomers: 10-25% by weight
-- ATE in the entire composition: 20-60% by weight, preferably 25-40%.
-- Thixotropic agent (preferably fumed silica) in the monomer/syrup fraction of the mixture:
0.10-3.5% or as much as necessary to obtain a viscosity of 1 to 10 Pa·s (1000 to 10,000 centipoise) (preferably
55 about 2.5 to 5 Pa·s (2,500 to 5,000 centipoise) after mixing and measured by Brookfield Viscometer Model RVTDV-
II, Spindle No. 2, 10 RPM.
-- Crosslinking agent as % by weight of the total monomers content: 0.01 to less than 0.5 when using ethylene glycol
dimethacrylate.

3
 EP 0 757 704 B1

-- Chain-transfer agent or chain terminator:

y parts by weight of chain terminator per 100 parts by weight of methylmethacrylate and x parts by weight of
crosslinking agent per 100 parts by weight of the monomers in the dispersion
wherein
5
x is 0.01 to less than 0.5 and
y is no greater than x + 0.2 and no less than 0.01.

[0015] In any event the chain transfer agent should not be present in amounts more than 1.2 times the concentration
10 of crosslinker. This amount may be adjusted to somewhat more or less when using chain-transfer agents other than
n-dodecyl mercaptan. A convenient way to compare the effects of chain-transfer agents is to compare molecular
weights obtained by polymerizing MMA in the presence of the chain-transfer agent and the absence of crosslinkers.
The MWm and MWn should be similar to that obtained by .01-0.5% n-dodecyl mercaptan.
[0016] In addition to the above-identified ingredients, dyes and pigments may be present, polymerization initiators
15 will be necessary, and other conventional ingredients may be used as are known in the art.
[0017] However, in the present invention, no particulates are used which are visibly distinguishable in the finished
product. Most synthetic granites contain visibly distinguishable particles of various compositions and colors ranging
from about 150 to 500µm (microns) - that is, they will pass through a sieve having openings of 500 µm (microns) and
be retained on one having openings of 150 µm (microns) (although larger particles are not uncommon in the synthetic
20 mineral art). It has been found that the objective of the present invention of even distribution of particles can be frustrated
through the use of such larger particles of various compositions, and accordingly, the particle size is restricted to
particles smaller than those which will be retained on a sieve having openings of 90 µm (microns), and preferably
smaller than those which will be retained on a sieve having openings of 60 µm (microns) according to the present
invention. These specifications for particle size apply in the present invention to particulates of any composition or
25 function-mineral flame retardants such as ATH, for example, or synthetic resin or other fillers.
[0018] The above-listed ingredients may be further described as follows:

PMMA as used herein is polymethylmethacrylate having a (weight average) molecular weight range of 30,000 to
600,000 having no crosslinked polymer chains, in order to remain soluble in MMA. It is typically made in situ by
30 partial polymerization of methyl methacrylate, but can be pre-polymerized and dissolved in the MMA.
MMA is methyl methacrylate. The syrup is described herein as comprising PMMA dissolved in monomers com-
prising at least 60% MMA, and preferably at least 80% MMA, but of course the crosslinking agent, chain terminator,
initiator, and thixotropic agent are also present in the amounts indicated herein as well as variable amounts of dyes
and/or pigments; in addition, small amounts of other, optional, copolymerizable monomers, notably butyl acrylate,
35 may be presen, in the syrup as is known in the art. It is preferred to use a syrup which contains 15% to 25% PMMA.
References to syrup herein and to MMA should be understood possibly to include such additional materials.

[0019] Alumina trihydrate is well known in the art of synthetic mineral manufacture. In the examples it has been used
in a particulate size range of about 9 µm (microns) average, but the particulate size may vary widely. As noted above,
40 the ATH as well as any other particles which are potentially visually distinguishable (if large enough) in the finished
product should be able to pass through a sieve having openings of 90 µm (microns), and preferably will pass through
a sieve having openings of 60 µm (microns), in order to assure that they will not be visually distinguishable. In quantity,
the ATH may vary from 20% to 60% weight (preferably 25% to 50%) of the finished product.
[0020] The present invention contemplates a solid surface material with the somewhat glossy appearance of the
45 acrylic matrix in which may be seen the effects of the particulates no greater than 90 µm (microns) across. The matenal
of the present invention is not simulative of granite, in that it is not coarse-grained, as granite is sometimes described.
Rather, if the effects of the particulates in the material of the present invention can be discerned at all, it may be
described as substantially fine-grained (which we define specifically as having grains or particles less than 90 µm
(microns) - that is, having no individually visibly discemable particles greater than 90 µm (microns). Herein, It is intended
50 for the term "substantially fine-grained" to include materials in which no grains or particles are individually visibly dis-
cernable.
[0021] Any number of crosslinking agents, di-functional or tri-functional, may be used. Examples for suitable
crosslinkers are ethylene glycol dimethylacrylate, propylene dimethylacrylate, polyethylene-glycol dimethylacrylate,
propylene dimethylacrylate, polyethylene-glycol dimethylacryalate, divinyl benzene, diallyl phthalate, 1,3-butanediol-
55 methacrylate, 1,4-butane ethylene glycol dimethacrylate or neopentyl glycol dimethacrylate as di-functional crosslink-
ers and trimethylol propane trimethacrylate,. triallyl cyanurate, pentaerythritol tetramethacrylate, allylmethacrylate, hy-
droxyethylmethacrylate or hydroxypropylmethacrylate as tri-functional crosslinkers. Most suitably, ethylene glycol
dimethacrylate is preferred. The crosslinking agents are maintained in low concentrations specifically 0.01 to less than

4
 EP 0 757 704 B1

0.5 parts by weight of di-functional crosslinkers based on 100 parts by weight of the MMA in the syrup, or, as a com-
ponent of the finished product, based on the crosslinked polymer. The combination of low concentrations of crosslinking
agents with the proper amount of chain terminator assures the appropriate polymeric network most amenable to ther-
moformability.
5 [0022] Chain terminators or chain-transfer agents, such as octyl mercaptan, iso-dodecyl mercaptan, thiurams, dithi-
ocarbarumates, dipentene dimercaptan, 2-mercapts ethanol, allyl mercapts-acetates, ethylene glycol dimercapts-ac-
etate, trimethylolethane trithioglycolate, pentaerythritol tetrathioglycolate, normally serve the function of regulating the
molecular weight of the polymerizing MMA, which in turn is known to affect the plastic behavior of polymerized mixture.
In accordance with our method, chain terminators or chain-transfer agents are used to regulate the length of the polymer
10 chains and thus to obtain the most suitable polymer matrix for thermoformability, as will be seen by the data in Example
3. They should be used in amounts from .01 to 0.7% weight of the total monomers present when using n-dodecyl
mercaptan.
[0023] While we may use a conventional thickening agent as well as a thixotropic agent, the thixotropic agents which
are used are shown herein to be particularly suited for present purposes. They appear to enhance the inertial tendency
15 of a particle to remain stationary in the matrix suspension. It is preferred to use fumed silica. By fumed silica there is
identified the product formed by the hydrolysis of silicon tetrachloride vapor in a flame of hydrogen and oxygen, to
produce solid particles in the range 7-30 nm (millimicrons). Many different types of fumed silica are available. To conduct
the bulk of the present experimentation, CAB-O-Sil M5 is selected, which has a surface area of 200 (sq.meter/gram)
m2/g. However, any conventional fumed silica will have a beneficial effect in the present invention.
20 [0024] The surface of fumed silica is hydrophilic since it has an abundance of hydroxyl groups, which makes it capable
of hydrogen bonding with suitable molecules. Absorbed moisture in the silica or in the other components has a gross
effect on the final viscosity of suspensions containing fumed silica and normally it lowers it. The same effect is given
by other substances which may be more or less capable of developing hydrogen bonding.
[0025] If the fumed silica and/or the ATH are dried to eliminate the adsorbed moisture, the final viscosity of the
25 suspension will be higher than when using the commercial products directly from the containers in which they are sold.
Drying of the ATH above 93°C (200°F) may defeat its primary utility as a flame retardant by depleting its water content.
[0026] In preferred compositions, the amount of fumed silica is selected so that the preferred viscosity is obtained,
regardless of variations in the other ingredients.
[0027] The preferred method of obtaining a desired viscosity is the following:
30
A. Mix all the ingredients (MMA, PMMA, ATH, pigments, other additives, catalysts, chain-transfer agent, and
crosslinking agent) of the formulation except the fumed silica and measure the viscosity as indicated below. If
necessary, adjust the MMA (monomer) content of the syrup to obtain a viscosity of (800 to 1,500 centipoise) 0.8
to 1.5 Pa·s.
35 B. Repeat step A including an amount of fumed silica and measure the viscosity.
C. Repeat step B to bring the viscosity to a level between 1 to 10 Pa·s (1000 to 10,000 centipoise). preferably
between (2,000 and 5,000 centipoise) 2 to 5 Pa·s.

[0028] As indicated previously, the stability of he syrup according to the present invention is considered important,
40 and this is especially so where the sheet or slab is formed in a continuous steel belt forming machine such as described
in Hellsund's U.S. Patent 3,371,383 and Opel's U.S. Patent 3,376,371, as these references represent the preferred
procedure of the present invention. While the forming of sheets or slabs between two moving continuous steel belts
is the preferred procedure, it is important to realize that such machines are necessarily prone to vibration and micro-
adjustments which tend to result in an almost unavoidable jostling of the particulates in the syrup; the concentrations
45 of crosslinker, chain terminator, fumed silica, and PMMA prepolymer are important in stabilizing the ATH and/or other
solids contributing to an evenly distributed fine-grained appearance.
[0029] The present invention is described in more detail below.
[0030] Figure 1A is a more or less hypothetical illustration of a prior art bending of a sheet of "Corian" 1.27 cm (one-
half inch) thick.
50 [0031] Figure 1B is a similar idealized illustration of the bending of a sheet of the present invention.
[0032] Referring now to Figure 1A, the recommended (DuPont "Corian" Technical Bulletin CTDC-110, October, 1987)
minimum bending radius of 7.62cm (three inches) for a prior art 1.27 cm (one-half inch) thick flat sheet is illustrated as
the radius of the bend in the inside curve from vertical extension point A to horizontal extension point B. Applying the
simple formula C=ΠD, the circumference of a hypothetical 7.62 cm (three-inch) circle would be 47,8780 cm (18.8496
55 inches), and the quarter circle AB would measure 11.9695 cm (4.7124 inches). Applying the same formula to the outside
curve for a sheet 1.27 cm (0.5 inch) thick, i.e. using a radius of 8.9 cm (3.5), yields a quarter circle of 13.958 cm
(5.4953), a difference of 16.6% from the inside curvature. Such a distortion will tend to cause a flow of heated ingredients
from the compressed inside curve to the expanded outside, and lengthwise toward points A and B from the curved

5
 EP 0 757 704 B1

portion. The flow of ingredients has a tendency to distort the visual or decorative pattern; accordingly, the prior art has
minimized the disruptions of the material by using a relatively large radius for the curvature, e.g. 7.62 cm (3 inches).
[0033] Figure 1B illustrates the achievable curvature of a sheet of the present invention, wherein the radius of the
curve is 1.27 cm (one-nalf inch) rather than the 7.62 cm (three inches) of the section of Figure 1A. In this case, the
5 theoretical circumference of the outside of the curved section CD is 100% greater than that of the inside of the curve.
It is readily seen that by enabling such a forming ability, the present invention overcomes a more severe displacement
of material in relatively less volume. The relatively more severe displacement of material means a greater potential for
distortion of the esthetic pattern, but such distortion is avoided or neutralized and so a continuity of pattern heretofore
not achievable under the stress of thermforming is achieved.
10 [0034] A test has been devised to evaluate thermoformability, which is a primary object of the present invention. The
test consists of clamping a flat test specimen 12.39 cm (4-7/8") square having the desired thickness onto a steel plate
in which has been drilled a 7.62 cm (3-inch) diameter hole; then a polished stainless steel plunger having a 2.54 cm
(one-inch) radius is lowered at a rate of 12.7 cm (five inches) per minute regardless of the resistance. The apparatus
and sample are heated prior to the test to the desired temperature. As the plunger moves, a load cell generates a
15 signal representing the amount of resistance in (pounds) N, wnich may be recorded. At the At the moment the specimen
ruptures, the plunger is stopped and the distance it has traveled is measured. Averaging of tests from four specimens
of each sample is recommended. This test may be referred to herein as TP-0085.

Example 1
20
[0035] A syrup was made by partial polymerization of MMA to obtain a viscosity of 3x10-3Pa·s (3 poise) and a PMMA
content in MMA of 20% by weight. In a vacuum rated vessel, 681 kg (1,500 lbs) of ATH OE-431 (by Solem) were added,
under agitation, to a mixture of 996 kg (2,194 lbs) of the syrup, 21.3 kg (47 lbs) of additional MMA and 4.253 kg of a
wetting agent for the ATH.
25 [0036] The mixture was agitated for 90 minutes under vacuum, while adding 2.024 kg of n-dodecyl mercaptan, 2.296
kg of ethylene glycol dimethacrylate and the necessary catalysts, pigments and additives to polymerize the mixture in
a continuous casting machine, as described by Hellsund in U.S. Patent 3,371,383 and Opel in U.S. Patent 3,376,371,
into a 1.27 cm (0.500") sheet.
[0037] The 2.024 kg n-dodecyl mercaptan represented 0.247% chain terminator based by weight on the available
30 MMA monomer; 2.296 kg ethylene glycol dimethacrylate represented 0.280% crosslinker based by weight on the avail-
able MMA monomer.
[0038] After complete curing, the 1.27 cm (one-half inch) thick product was cut into four square specimens as required
by the above-described test procedure TP-0085 and was tested for thermoformability, along with four specimens each
of the commercial materials indicated in Table I. Results reported are the averages of the four specimens in each case.
35

40

45

50

55

6
 EP 0 757 704 B1

10

15

20

25

30

35

40

45 [0039] It will be seen from the above results that the polyester materials, Avonite Class I and Surrell/Frost, were quite
brittle and broke into small pieces. The Formstone PMMA from Avonite and the Corian PMMA were also rather un-
yielding and not at all suitable for the thermoforming into convex or concave molds by vacuum.

Thermoforming Example No. 1

50
Part A

[0040] A separate piece of 1.27 cm (0.500") thick sneet produced in Example 1 was identified as TFA Sample 2404
and was thermoformed in a sink vanity mold of overall dimensions 44.45 x 71.44 cm (17-1/2" x 28-1/8"), where the
55 opening of the sink was about 25.72 cm x 39.05 cm (10-1/8" x 15-3/8") and the deepest part of the sink was about
15.56 cm (6-1/8") from the flat surface. The flat surface formed a bull nose with a curvature of 0.40 cm (5/32") of radius
in the front and had a 90° back splash wall of about 12.7 cm (5") of height, with a curvature radius at the 90° bend of
1.27 cm (1/2").

7
 EP 0 757 704 B1

[0041] Thermoforming tests were performed by heating a sheet to the desired temperature in a standard vacuum
thermoforming machine with top and bottom side heater banks. Once the sheet reached the desired temperature, it
was lowered into the concave sink mold and vacuum was applied to pull the sheet onto the mold surfaces. A wide
range of thermoforming temperatures was examined, at 5.5°C (10°F) intervals.
5 [0042] The best thermoforming temperature to obtain good details in the finished part was in the 148.9-176.7°C
(300°-350°F) range.

Part B

10 [0043] TFA Sample 2404 was also tested by the thermoformability test TP-0085, described above, at the selected
temperatures listed below. The results were:

Temp °C (°F) cm (Inches) at Break N (Lbs. Force) at Break

15
143.3 (290) 15.24 (6.0) 956.32 (215)
148.9 (300) 17.02 (6.7) 796.19 (179)
154.4 (310) 17.53 (6.9) 760.61 (171)
160.0 (320) 18.23 (7.2) 618.27 (139)
165.5 (330) 19.05 (7.5) 467.04 (105)
20 171.1 (340) 19.05 (7.5) 418.11 (94)
176.6 (350) 11.94 (4.7) 217.95 (49)
182.2 (360) 10.67 (4.2) 133.44 (30)

[0044] The observations about the best thermoforming temperature for molding sinks [148.9-176.7°C (300-350°F)]
25
correlate well with the " cm (Inches) at Break" results, as long as the force at break remains below about 1000 N (225
lbs), preferably 889.6 N (200 lbs). This is important because in our preferred thermoforming arrangement, where the
heated sheet is pulled by vacuum onto the convex or concave mold surface, it is desirable to accomplish the task at
"partial vacuum pressures", that is 26.1-48.5 kPa (8-15 inches of vacuum) rather than stronger vacuums. The present
invention enables the use of far less stressful vacuums than otherwise may be the case, so that the lifetime of the mold
30
is significantly lengthened.

Example 2

[0045] TFA samples were prepared with the same basic formulation of Example 1 and TFA Sample 2404, except for
35
the amount of ATH, which was varied as listed below. The polymer matrix (MMA, I-3, syrup, chain transfer and crosslink-
ing agents, catalysts, etc.) was adjusted accordingly to compensate for the increase or decrease in the amount of ATH.
See Thermoforming Example No. 2 for the amounts of ATH used.

Thermoforming Example No. 2

40

[0046] The samples listed below were prepared as described in Example 2 and were tested according to TP-0085
at 171.1°C (340°F) for 40 minutes and per ASTM E-84 Tunnel Test. In the E-84 test, the F.S.I. value is the Flame
Spread Index and the S.I. is the Smoke Index. The results show how increasing amounts of ATH and the corresponding
decreasing amounts of polymer matrix do not significantly affect the heat distortion temperature and the thermoforming
45
characteristics, but they do affect the Flame Spread Index (F.S.I.) and the Smoke Index (S.I.).

50

55

8
 EP 0 757 704 B1

10

15

20

25

30

35

40

45 Example 3

[0047] A formulation similar to the one described in Example 1 was prepared in the laboratory and poured between
two casting plates made of stainless steel, to produce 30.48 cm x 30.48 cm (12" x 12") sheets of 1.27 cm (0.500")
thickness after curing. The curing was obtained by dipping the stainless steel plate assembly into a water tank kept at
50 82.2°C (180°F) for one hour and then into an air circulating oven, kept at 121.1°C (250°F) for one hour. This was done
to evaluate laboratory prepared formulations in which variations of the amount of chain transfer (n-dodecyl mercaptan)
and crosslinking agents (ethylene glycol dimethacrylate) were made.
[0048] The formulation consisted of 45 parts of Solem OE-431 ATH having an average size of 9 µm (microns), added
under agitation to a mixture of 52 parts of syrup (the syrup was MMA containing about 20% PMMA), 2.75 parts of
55 additional MMA, and 0.25 parts of a wetting agent for the ATH. To the mixture were added various amounts of chain-
transfer agent (n-dodecyl mercaptan) and crosslinking agent (ethylene glycol dimethacrylate) in the quantities shown
in the table listed in Thermoforming Example No. 3. These quantities are listed in parts per hundred over the total
amount of methyl methacrylate in the formulation.

9
 EP 0 757 704 B1

[0049] After addition of catalysts, pigments, additives, and deaeration under vacuum, to avoid bubbles in the sheet,
the mixture was polymerized between casting plates as indicated above.

Thermoforming Example No. 3

5
[0050] A number of samples prepared as described in Example No. 1 in 1.27 cm (0.500") thickness, were tested by
the thermoforming test method TP-0085, 40 minutes at 171.1°C (340°F). The details of the compositions and the
results are listed below:

10

15

20

25

30

35

40

45

50
[0051] From this table it will be seen that the best results were obtained at the Sample 43A levels of chain-transfer
and crosslinking agent. In general, increasing amounts of crosslinker increase the force needed for the forming. This
is demonstrated well by samples 43A, 33C, and 33D. Some chain-transfer agent is better than none: see Samples
33A, 33B and 43A. Larger amounts of both may provide satisfactory results, but the amount of stretch available is
55 limited, see Samples 33E and 43A. When the amount of chain-transfer agent is too high, severe degradation may take
place, see Samples 43B and 43A. Sample 43C did not exhibit the severe degradation of Sample 43B, but it did not
appear to possess a sufficient thermal stability and would not be recommended. If the amount of crosslinker is too low,
the preferred level of chain-transfer agent may be relatively too high and cause gross thermal degradation, as shown

10
 EP 0 757 704 B1

by Samples 43D and 43E against Sample 43A.

[0052] Therefore, 0.01 mole percent to about 0.6 mole percent di-functional crosslinker per mole of methyl methacr-
ylate (MMA) and other monomer (preferably about 0.15 to about 0.5), and 0.01 to less than 0.5 parts by weight chain-
transfer agent per 100 parts MMA monomer, preferably 0.01 to 0.3 parts per hundred, are used according to the present
5 invention.

Example 4

[0053] The samples described in Example 2 and Thermoforming Example No. 2 were heated in an oven with forced
10 air circulation. Other specimens of the same samples were thermoformed using a square box mold, concave config-
uration, of such dimensions that the flat section of the thermoformed part was half of the thickness of the original
sample. The Delta E color difference of the thermoformed sample was measured in Cielab units against the corre-
sponding samples which had been heated only. Note: The Cielab color system is the commonly used name for the
CIE 1976 L*a*b* system. Here a spectrophotometer SpectraSensor II, by ACS was used.
15

Sample I.D. Color Delta E (A) Delta E (B)

TFA No. 2485 Cameo 1.8 3.3
TFA No. 2404 Porcelain 1.4 1.8
20 TFA No. 2405 Cameo 2.0 2.8
TFA No. 2406 Almond 4.6 6.2
(A) Heated 20 mins. at (340°F) 171.1°C.
(B) Heated 30 mins. at (340°F) 171.1°C.

25 Comment: When Delta E is higher than 2.0, the human eye may perceive a color change that makes the part unac-
ceptable. The color change is more or less noticeable depending on the color of the part. The Delta E or color changes
of the same thermoformed parts are proportional to the amount of time the sheet is heated -- see the difference between
data of (A) and (B) columns. They are also proportional to the amount of stretching or thinning of the sheets (data not
shown) and to the initial color of the sheet: sample TFA 2406 changes much more than the other colors. Personal
30 preference may dictate a case-by-case evaluation, depending on the color of the sheet, the heating time/source se-
lected and the type of mold, but it is also evident that the sheets of our invention can be thermoformed into shapes
where the maximum color difference remains below the level of 2.0 units in the Cielab system.

Example 5
35

[0054] Sheet samples of 1.27 cm (.500") thickness were prepared by the laboratory method described in Example
3, from a basic formulation consisting of:

% Weight
40
ATH (Solem OE-431) 40
Syrup 59.75
BYK 1142 .25
n-dodecyl mercaptan 0.138phr(*)
45
ethylene glycol dimethacrylate 0.157phr(*)
catalysts As needed
pigments As needed
other additives As needed
50 (*)these amounts represent .289% and .328%, respectively, of the MMA present in the formulation.

[0055] Sample 5A was made as described above. Sample 5B had 0.5phr of Cab-O-Sil M5 (by Cabot Corporation)
added to the mixture described above. Sample 5B exhibited a viscosity of 3.0 Pa·s (3,000 centipoise) while sample
5A was rated at 1.06 Pa·s (1,060 centipoise). The measurements were obtained from a Brookfield Viscometer, Model
55 RVTDV-II, Spindle No. 2, at 10 RPM.
[0056] The impact resistance in cm/kg (inches/lbs.) was measured by ASTM D-3029 (Gardner method).

11
 EP 0 757 704 B1

Sample I.D. Top Side Impact Resistance Bottom Side Impact Resistance
5A 200.3 (35.8) 288.7 (51.6)
5 5B 232.8 (41.6) 245.1 (43.8)

[0057] Achieving the same impact resistance on both sheet sides demonstrates that the material is homogeneous.
If the ATH settles toward the bottom side of the sheet during its production process, the top surface side will be richer
in polymer. This was the case with sample 5A. Under the conditions of the test, the initial rupture occurs on the lower
10 side, and sample 5A displayed its relative weakness by failing when impacted on the top. When another sample of 5A
was impacted on the ATH-rich side, the impact resistance was higher. But in the case of 5B, the sides had approximately
equal results, demonstrating the invention.
[0058] Thereby it has been shown that the fumed silica is able to adjust the viscosity or thixotropicity of the completed
syrup so the ingredients will remain evenly distributed throughout the thickness of the sheet during the relatively long
15 curing period. As indicated elsewhere herein, an even distribution of ingredients over the cross-section or profile of a
sheet or slab permits an esthetic continuity of pattern, color, or design when the sheet is manipulated by thermoforming
or juxtaposed during fabrication. But uneven distribution does not necessarily result in undesirable mechanical ther-
moforming properties -- that is, the presence of polymer-rich and ATH-rich sides of a sheet does not significantly
adversely affect the TP-0085 test results, as may be seen elsewhere herein.
20 [0059] A preferred composition for its combined properties of composition uniformity and thermoformability, based
on the results particularly of Examples 3 and 5 contains 0.2% to 0.35% chain-transfer agent, 0.25 to 0.4% crosslinking
agent, and 0.2% to 1.5% fumed silica.

Example 6
25
[0060] Sheet samples of 1.27 cm (.500") thickness were prepared by the laboratory method described in Example
3, from a basic formulation consisting of:

% Weight
30
ATH (Solem OE-431) 40
MMA/PMMA (20%) Syrup 59.75
BYK 1142 .25
n-dodecyl mercaptan 0.119phr(*)
35 ethylene glycol dimethacrylate 0.135phr(*)
catalysts As needed
pigments As needed
other additives As needed
(*)These amounts correspond to .249% and .282%, respectively, of the MMA present in the formulation.
40

[0061] Samples 6A, 6B, and 6C were made from the formulation above, with Epoxol 9.5 (epoxidized linseed oil
produced by ACS, Inc.) added as indicated in the table below.
[0062] Samples 6D, 6E, and 6F were prepared from the same formulation above, but samples 6E and 6F included
45 2phr (parts by weight per hundred) of Butyl Acrylate and 6F included 2phr Butyl Acrylate plus 1.2phr of Cab-O-Sil M5
fumed silica.
[0063] Samples 6G and 6H contained 2 and 4phr, respectively, of Fyrol RDP, a flame retardant additive containing
phosphorus and sold by AKZO Corporation.

50

55

12
 EP 0 757 704 B1

10

15

20

25

30

35

40

45
[0064] Examples 6A, 6B, and 6C show a higher degree of stretch of the sheet at a lower force.
[0065] In Examples 6D, 6E, and 6F the same is achieved by adding butyl acrylate, a comonomer chosen from those
known to lower the Tg of PMMA, so that a given formulation will have a "more pliable polymer matrix" when the tem-
perature and all other conditions are the same. In Examples 6G, 6H a commercial flame retardant added to the for-
50 mulation shows how the thermoforming parameters can be modified while adding flame retardant additives which might
be categorized as plasticizers.
[0066] Epoxol 9.5 is an epoxidized linseed oil, sold by Swift Chemical Company. Fyrol RDP is a bis-phosphate ester,
containing 11% of phosphorus and it is sold by AKZO.

55 Example 7

[0067] The effect of other fillers, and different grades of ATH was examined by preparing (0.500") 1.27 cm samples
by the method described in Example 5 for sample 5A. A fine grade of ATH, Micral 1000 by Solem Corporation, average

13
 EP 0 757 704 B1

particle size 1 micron, was used in sample 7A. The ratio of MMA/syrup was adjusted to a higher level of MMA, to
maintain a workable viscosity of the mixture before polymerization. In sample 7B, OE-431CM (by Solem Corporation),
a surface treated grade of ATH was used.
[0068] In sample 7C, 10 parts of ATH were replaced by Calcium Carbonate, as a mixture made from 188 grams of
5 CaCO3, ACS grade by Fisher, and 42 grams of CaCO3 #10 by Georgia Marble.

TP-0085 at 171.1°C (340°F) 40 min.

Sample I.D. cm (Inches) at Break N (Lbs. Force) at Break
10 7A 11.9 (4.7) 636.1 (143)
7B 10.9 (4.3) 164.6 (37)
7C 10.7 (4.2) 146.8 (33)

It is evident that other ATH types and other mineral fillers may be used and that satisfactory thermoforming properties
15
are retained.

Example 8

[0069] The addition of another polymer matrix material to the PMMA matrix was examined by adding a general
20
purpose polyester resin (MR-12845, manufactured by Aristech Chemical Corporation) to the formulation described in
Example 5A. The PE resin replaced the same amount of the MMA/syrup fraction.

TP-0085 at 171.1°C (340°F) 40 min.

25 Sample I.D. % PE Resin cm (Inches) at Break (Lbs. Force) N at Break
8A 10 5.3 (2.1) (180) 800.6
8B 20 2.0 (0.8) (94) 418.1

30 The addition of other monomer/polymer systems will affect the degree of thermoformability depending on the type of
polymer backbone used. Large amounts of a thermoset resin, as the one used above, may reduce the degree of
thermoformability, but it may provide for a higher service life temperature of the part to be made.

35 Claims

1. A composition for making a thermoformable sheet or slab comprising

(a) a syrup comprising at least 60% of methyl methacrylate having dissolved within it 10% to 25% uncrosslinked
40 polymethylmethacrylate having a weight average molecular weight in the range of 30,000 to 600,000, said
syrup having dispersed within it y parts by weight of chain terminator per 100 parts by weight of methylmeth-
acrylate and x parts by weight of crosslinking agent per 100 parts by weight of the monomers in the dispersion
wherein

45 x is 0.01 to less than 0.5 and

y is no greater than x + 0.2 and no less than 0.01; and

b) solid particulates which will pass through a sieve having openings of 90 µm (microns), said solid particulates
comprising 20% to 60%, based on the weight of the final composition, alumina trihydrate.
50
2. The composition of claim 1, wherein x is a number from 0.25 to 0.4.

3. The composition of claim 1, wherein y is a number from 0.2 to 0.35.

55 4. The composition of claim 1, wherein said solid particulates will pass through a sieve having openings of 60 µm
(microns).

5. The composition of claim 1, further comprising

14
 EP 0 757 704 B1

(c) a thixotropic agent in the monomer syrup fraction in an amount which is sufficient to obtain a viscosity of the
syrup of 1 to 10 Pa·s (1000 to 10,000 centipoise).

6. A method of making a thermoformable synthetic mineral sheet or slab comprising

5
(1) preparing a syrup of uncrosslinked polymethylmethacrylate having a weight average molecular weight in
the range of 30,000 to 600,000 dissolved in ethylenically unsaturated monomers of which at least 60% by
weight are methyl methacrylate,
(2) adding to and dispersing within said syrup
10
(a) y parts by weight of chain terminator per 100 parts by weight of methylmethacrylate and x parts by
weight of crosslinking agent per 100 parts by weight of the monomers in the dispersion
wherein

15 x is 0.01 to less than 0.5 and

y is no greater than x + 0.2 and no less than 0.01; and

(b) solid particulates which will pass through a sieve having openings of 90 µm (microns), said solid par-
ticulates comprising 20% to 60%, based on the weight of the final composition, alumina trihydrate,
20
(3) confining said syrup in a sheet forming mold, and
(4) polymerizing said ethylenically unsaturated monomers in said syrup in the presence of said crosslinking
agent and said chain terminator to form a solid sheet having a substantially fine-grained appearance.

25 7. The method of claim 6, wherein the amount of alumina trihydrate present is 25% to 40% of the final composition.

8. The method of claim 6, wherein x is a number from 0.25 to 0.4 and y is a number from 0.2 to 0.35.

9. The method of claim 6, wherein said solid particulates will pass through a sieve having openings of 60 µm (microns).
30
10. The method of claim 6, further comprising adding and dispersing within said syrup (c) sufficient fumed silica to
obtain a viscosity of the syrup of 1 to 10 Pa·s (1000 to 10,000 centipoise).

11. The method of claim 5, wherein the amount of fumed silica added in step (2)(c) is sufficient to obtain a viscosity
35 of 2.5 to 5 Pa·s (2,500 to 5,000 centipoise).

12. The method of claim 6, wherein said steps (3) and (4) take place in a sheet or slab forming machine comprising
two continuous steel belts.

40 13. A substantially fine-grained thermoformable sheet or slab made by confining a composition of claim 1 in a sheet
or slab forming mold and polymerizing said methyl methacrylate in the presence of said crosslinking agent and
said chain terminator.

14. A substantially fine-grained therformable sheet or slab obtainable by the method of any of claims 6 to 12.
45

Patentansprüche

1. Eine Zusammensetzung zur Herstellung einer wärmeformbaren Folie oder Platte, umfassend
50
(a) einen Sirup, umfassend mindestens 60 % Methylmethacrylat mit 10 % bis 25 % darin gelöstem, unvemetz-
tem Polymethylmethacrylat mit einem gewichtsmittleren Molekulargewicht in dem Bereich von 30000 bis
600000, wobei in dem Sirup y Gew.-Teile Kettenabbrecher pro 100 Gew.-Teile Methylmethacrylat und x Gew.-
Teile Vernetzungsmittel pro 100 Gew.-Teile der Monomeren in der Dispersion dispergiert sind,
55 worin

x 0,01 bis weniger als 0,5 ist, und

y nicht größer als x + 0,2 und nicht kleiner als 0,01 ist; und

15
 EP 0 757 704 B1

(b) feste Teilchen, die durch ein Sieb mit Öffnungen von 90 µm (Mikron) hindurch gehen, wobei die festen
Teilchen 20 bis 60 % Aluminiumoxid-Trihydrat, bezogen auf das Gewicht der Endzusammensetzung, umfas-
sen.

5 2. Die Zusammensetzung nach Anspruch 1, worin x eine Zahl von 0,25 bis 0,4 ist.

3. Die Zusammensetzung nach Anspruch 1, worin y eine Zahl von 0,2 bis 0,35 ist.

4. Die Zusammensetzung nach Anspruch 1, worin die festen Teilchen durch ein Sieb mit Öffnungen von 60 µm (Mi-
10 kron) hindurch gehen.

5. Die Zusammensetzung nach Anspruch 1, umfassend weiterhin

(c) ein thixotropes Mittel in der Monomersirupfraktion in einer Menge, die ausreichend ist, um eine Viskosität des
Sirups von 1 bis 10 Pa·s (1000 bis 10000 Centipoise) zu erhalten.
15
6. Ein Verfahren zur Herstellung einer wärmeformbaren, synthetischen, Mineralfolie oder Platte, umfassend

(1) das Herstellen eines Sirups aus unvemetztem Polymethylmethacrylat mit einem gewichtsmittleren Mole-
kulargewicht in dem Bereich von 30000 bis 600000, gelöst in ethylenisch ungesättigten Monomeren, von
20 denen wenigstens 60 Gew.-% Methylmethacrylat sind,

(2) das Zugeben zu und das Dispergieren in dem Sirup von

(a) y Gew.-Teilen Kettenabbrecher pro 100 Gew.-Teile Methylmethacrylat und x Gew.-Teilen Vemetzungs-
25 mittel pro 100 Gew.-Teile der Monomeren in der Dispersion,
worin

x 0,01 bis weniger als 0,5 ist, und

y nicht größer als x + 0,2 und nicht kleiner als 0,01 ist; und
30
(b) festen Teilchen, die durch ein Sieb mit Öffnungen von 90 µm (Mikron) hindurch gehen, wobei die festen
Teilchen 20 bis 60 % Aluminiumoxid-Trihydrat, bezogen auf das Gewicht der Endzusammensetzung, um-
fassen,

35 (3) das Einschließen des Sirups in eine folienbildende Form und

(4) das Polymerisieren der ethylenisch ungesättigten Monomeren in dem Sirup in Gegenwart des Vemet-
zungsmittels und des Kettenabbrechers, um eine feste Folie mit einem im Wesentlichen feinkörnigen Ausse-
hen zu bilden.
40
7. Das Verfahren nach Anspruch 6, worin die Menge des vorhandenen Aluminiumoxid-Trihydrats 25 bis 40 % der
Endzusammensetzung ausmacht.

8. Das Verfahren nach Anspruch 6, worin x eine Zahl von 0,25 bis 0,4 ist, und y eine Zahl von 0,2 bis 0,35 ist.
45
9. Das Verfahren nach Anspruch 6, worin die festen Teilchen durch ein Sieb mit Öffnungen von 60 µm (Mikron)
hindurch gehen.

10. Das Verfahren nach Anspruch 6, weiter umfassend das Zugeben und das Dispergieren in dem Sirup von (c) einer
50 Menge an Quarzstaub, die ausreichend ist, um eine Viskosität des Sirups von 1 bis 10 Pa•s (1000 bis 10000
Centipoise) zu erhalten.

11. Das Verfahren nach Anspruch 5, worin die Menge an in der Stufe (2) (c) zugesetztem Quarzstaub ausreichend
ist, um eine Viskosität von 2,5 bis 5 Pa•s (2500 bis 5000 Centipoise) zu erhalten.
55
12. Das Verfahren nach Anspruch 6, worin die Stufen (3) und (4) in einer Folien oder Platten bildenden Maschine
stattfindet, die zwei kontinuierliche Stahlbänder enthält.

16
 EP 0 757 704 B1

13. Eine im Wesentlichen feinkörnige, wärmeformbare Folie oder Platte, hergestellt durch Einschließen einer Zusam-
mensetzung nach Anspruch 1 in einer Folie oder Platte bildenden Form und Polymerisieren des Methylmethacry-
lats in Gegenwart des Vernetzungsmittel und des Kettenabbrechers.

5 14. Eine im Wesentlichen feinkörnige, wärmeformbare Folie oder Platte, erhältlich durch das Verfahren nach einem
der Ansprüche 6 bis 12.

Revendications
10
1. Composition pour produire une plaque ou dalle thermoformable comprenant

(a) un sirop comprenant au moins 60 % de méthacrylate de méthyle dans lequel sont dissous 10 % à 25 %
de poly(méthacrylate de méthyle) non réticulé ayant une masse moléculaire moyenne en poids dans le do-
15 maine de 30 000 à 600 000, ledit sirop contenant à l'état dispersé y parties en masse d'agent de terminaison
de chaîne pour 100 parties en masse de méthacrylate de méthyle et x parties en masse d'agent de réticulation
pour 100 parties en masse des monomères dans la dispersion
où

20 x est 0,01 à moins de 0,5 et

y n'est pas supérieur à x + 0,2 et pas inférieur à 0,01 ; et

(b) des matières particulaires solides qui traversent un tamis ayant des ouvertures de 90 µm (micromètres),
lesdites matières particulaires solides comprenant 20 % à 60 %, par rapport à la masse de la composition
25 finale, d'alumine trihydratée.

2. Composition selon la revendication 1, où x est un nombre de 0,25 à 0,4.

3. Composition selon la revendication 1, où y est un nombre de 0,2 à 0,35.

30
4. Composition selon la revendication 1, où lesdites matières particulaires solides traversent un tamis ayant des
ouvertures de 60 µm (micromètres).

5. Composition selon la revendication 1, comprenant en outre

35 (c) un agent thixotrope dans la fraction de sirop de monomères en une quantité qui est suffisante pour obtenir
une viscosité du sirop de 1 à 10 Pa.s (1 000 à 10 000 centipoises).

6. Procédé de production d'une plaque ou dalle minérale synthétique thermoformable comprenant

40 (1) la préparation d'un sirop de poly(méthacrylate de méthyle) non réticulé ayant une masse moléculaire
moyenne en poids dans le domaine de 30 000 à 600 000 dissous dans des monomères éthyléniquement
insaturés dont au moins 60 % en masse sont du méthacrylate de méthyle,
(2) l'addition audit sirop et la dispersion dans ledit sirop

45 (a) de y parties en masse d'agent de terminaison de chaîne pour 100 parties en masse de méthacrylate
de méthyle et de x parties en masse d'agent de réticulation pour 100 parties en masse des monomères
dans la dispersion.
où

50 x est 0.01 à moins de 0,5 et

y n'est pas supérieur à x + 0,2 et pas inférieur à 0,01 ; et

(b) de matières particulaires solides qui traversent un tamis ayant des ouvertures de 90 µm (micromètres),
lesdites matières particulaires solides comprenant 20% à 60 %, par rapport à la masse de la composition
55 finale, d'alumine trihydratée,

(3) le confinement dudit sirop dans un moule de formation de plaque, et

(4) la polymérisation desdits monomères éthyléniquement insaturés dans ledit sirop en présence dudit agent

17
 EP 0 757 704 B1

de réticulation et dudit agent de terminaison de chaîne pour former une plaque solide ayant un aspect sensi-
blement à grains fins.

7. Procédé selon la revendication 6, où la quantité d'alumine trihydratée présente est de 25 % à 40 % de la compo-

5 sition finale.

8. Procédé selon la revendication 6, où x est un nombre de 0,25 à 0,4 et y est un nombre de 0,2 à 0,35.

9. Procédé selon la revendication 6, où lesdites matières particulaires solides traversent un tamis ayant des ouver-
10 tures de 60 µm (micromètres).

10. Procédé selon la revendication 6, comprenant en outre l'addition et la dispersion dans ledit sirop (c) d'une quantité
suffisante de silice fumée pour obtenir une viscosité du sirop de 1 à 10 Pa.s (1 000 à 10 000 centipoises).

15 11. Procédé selon la revendication 5, où la quantité de silice fumée ajoutée dans l'étape (2)(c) est suffisante pour
obtenir une viscosité de 2,5 à 5 Pa.s (2 500 à 5 000 centipoises).

12. Procédé selon la revendication 6, où lesdites étapes (3) et (4) ont lieu dans une machine de formation de plaques
ou de dalles comprenant deux bandes d'acier continues.
20
13. Plaque ou dalle thermoformable sensiblement à grains fins produite par confinement d'une composition selon la
revendication 1 dans un moule de formation de plaques ou de dalles et polymérisation dudit méthacrylate de
méthyle en présence dudit agent de réticulation et dudit agent de terminaison de chaîne.

25 14. Plaque ou dalle thermoformable sensiblement à grains fins qui peut être obtenue par le procédé selon l'une quel-
conque des revendications 6 à 12.

30

35

40

45

50

55

18
EP 0 757 704 B1

19